Novel comb copolymer and process for the preparation thereof

ABSTRACT

A comb polymer of which the backbone is 2-acrylamido-2-methylpropanesulfonic acid, onto which poly(N-alkylacrylamide) or poly(N,N-dialkylacrylamide) lateral segments are grafted; process for the preparation thereof comprising: a step (a) of reacting a compound of formula (II) with a compound of formula (III), in a (tert-butanol)-water mixture, so as to obtain a poly(N-alkylacrylamide) or poly(N,N-dialkylacrylamide) telomere of formula (I); a step (c) of reacting, in tert-butanol, the telomer of formula (I) obtained in step (a), with an acid chloride of formula (IV) so as to obtain a solution of the macromonomer of formula (V); a step (e) of copolymerising, in tert-butanol, the macromonomer of formula (V) resulting from step (c), with the ammonium salt of 2-acrylamido-2-methylpropanesulfonic acid and, if desired, a step (f) of purifying the comb polymer obtained in step (e).

The present patent application has as subject matter a novel process for the preparation of water-soluble grafted copolymers.

Heat-thickening polymers are polymers, the viscosity of which varies considerably as a function of the temperature. They are characterized in particular by a “critical” temperature, above which the viscosity of their aqueous solution very markedly increases, generally by a factor of several tens.

International application WO 00/40958 describes a process for the preparation of copolymers of acrylamide and of poly(N-isopropylacrylamide) which includes the following successive stages:

(a) the synthesis of an N-isopropylacrylamide (NIPAM) telomer by radical polymerization; (b) isolation of the telomer obtained, (PNIPAM)_(x)-NH₂, by precipitation from ether, filtration and then drying; (c) the reaction in methylene chloride of (PNIPAM)_(x)-NH₂ with a large excess acrylic acid in the presence of cyclohexylcarbodiimide to result in the poly(NIPAM) macro-monomer carrying an acryloyl functional group at the (PNIPAM)_(x) chain end; (d) the isolation of the macromonomer obtained by precipitation from ether, filtration and then drying; (e) the copolymerization of the macromonomer obtained with acrylamide (AM) or dimethylacrylamide (DMA) in water, in order to obtain the grafted copolymers comprising a (PNIPAM)_(x) segment, AM-g-(PNIPAM)_(x) or DMA-g-(PNIPAM)_(x); (f) the purification by precipitation from water for DMA/(PNIPAM)_(x) or from acetone for AM/(PNIPAM)_(x), followed by ultrafiltration.

The international application published under the number WO 2007/000535 discloses a process for the preparation of grafted polymers, while limiting as much as can be done the use of organic solvents, and more particularly a process for the preparation of a comb copolymer, the backbone of which is of the acrylamide, acrylic acid, acryloylaminoethanol or dimethylacrylamide type, to which poly(N-alkylacrylamide) or poly(N,N-dialkylacrylamide) side segments are grafted, comprising the following successive stages:

(a) the preparation of a poly(N-alkylacrylamide) or poly(N,N-dialkylacrylamide) telomer, of formula (I):

H₂N—R₁—Z—{CH₂—C(R₂)[C(═O)N(R₃)(R₄)]—}_(n)—H   (I)

in which n represents an integer greater than or equal to 2 and less than or equal to 100, Z represents a functional group capable of acting as radical transfer agent, R₁ represents a divalent radical comprising from 1 to 4 carbon atoms, R₂ represents a hydrogen atom or a methyl radical, R₃ represents a hydrogen atom or a linear or branched alkyl radical comprising from 1 to 4 carbon atoms and R₄, which is identical to or different from R₃, represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, by reaction in water of a compound of formula (II):

CH₂═C(R₂)—C(═O)N(R₃)(R₄)   (II)

in which R₂, R₃ and R₄ are as defined above, with a chain-limiting compound of formula (III):

Z—R₁—NH₂   (III)

in which Z represents a functional group capable of acting as radical transfer agent, in a (II)/(III) molar ratio of less than or equal to n and greater than or equal to n/10, in the presence of a polymerization initiator;

(b) the isolation of the telomer of formula (I) obtained in stage (a);

(c) the reaction in water of the telomer of formula (I) obtained in stage (b) with the acid chloride of formula (IV):

CH₂═C(R₅)—C(═O)—Cl   (IV)

in which R₅ represents a hydrogen atom or a methyl radical and in a (IV)/(III) molar ratio of less than or equal to 10 and greater than or equal to 1, while maintaining the pH of the reaction medium at a value of between 6 and 13 and preferably between 7 and 8, in order to obtain a macromonomer of formula (V):

CH₂═C(R₅)—C(═O)NH—R₁—Z—{CH₂—C(R₂)[C(═O)N(R₃)(R₄)]—}_(n)—H   (V)

(d) the isolation of the macromonomer of formula (V) obtained in stage (c);

(e) the copolymerization in water of the macromonomer of formula (V) isolated in stage (d) with a monomer chosen from acrylamide, acrylic acid, acryloylaminoethanol or dimethylacrylamide and, if desired;

(f) the purification of the comb copolymer obtained.

In point of fact, while the process thus disclosed operates perfectly when the main backbone is composed of a sequence of neutral monomers, it is not the same when it is desired to replace these neutral monomers with ionic monomers, such as acrylic acid or 2-acrylamido-2-methylpropanesulfonic acid (ATBS). This is because a salting out phenomenon occurs, which results in the polymerization of the macromonomer intended to form the pendant chains, such as the poly(N-isopropylacrylamide) macromonomer.

The inventors have thus attempted to develop a process which does not exhibit the disadvantage set out above.

For this reason, according to a first aspect, a subject matter of the invention is a process for the preparation of a comb copolymer, the backbone of which is of the 2-acrylamido-2-methylpropanesulfonic acid (ATBS) type, to which poly(N-alkylacrylamide) or poly(N,N-dialkylacrylamide) side segments are grafted, characterized in that it comprises the following successive stages:

a stage (a) of reaction of a compound of formula (II):

CH₂═C(R₂)—C(═O)—N(R₃)(R₄)   (II)

in which R₂ represents a hydrogen atom or a methyl group, R₃ represents a hydrogen atom or a linear or branched alkyl radical comprising from 1 to 4 carbon atoms and R₄, which is identical to or different from R₃, represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, with a chain-limiting compound of formula (III):

Z—R₁—NH₂   (III)

in which R₁ represents a divalent radical comprising from 1 to 4 carbon atoms and Z represents a functional group capable of acting as radical transfer agent, in the presence of a polymerization initiator, in a tert-butanol/water mixture, in order to obtain a poly(N-alkylacrylamide) or poly(N,N-dialkylacrylamide) telomer of formula (I):

H₂N—R₁—Z—{CH₂—C(R₂)[C(═O)N(R₃)(R₄)]—}_(n)—H   (I)

in which n represents an integer greater than or equal to 2 and less than or equal to 100 and Z represents a functional group capable of acting as radical transfer agent; optionally

a stage (b) of isolation and/or of drying of said telomer of formula (I) obtained in stage (a);

a stage (c) of reaction in tert-butanol of the telomer of formula (I) obtained in stage (a) or optionally in stage (b) with an acid chloride of formula (IV):

CH₂═C(R₅)—C(═O)—Cl   (IV)

in which R₅ represents a hydrogen atom or a methyl radical, in a (IV)/(III) molar ratio of less than or equal to 10 and greater than or equal to 1, while maintaining the pH of the reaction medium at a value of between 8 and 10, in order to obtain a solution of the macromonomer of formula (V):

CH₂═C(R₅)—C(═O)NH—R₁—Z—{CH₂—C(R₂)[C(═O)N(R₃)(R₄)]—}_(n)—H   (V)

optionally

a stage (d) of isolation and/or of drying of said macromonomer of formula (V) obtained in stage (c);

a stage (e) of copolymerization in tert-butanol of the macromonomer of formula (V) resulting from stage (c) or from stage (d) with the ammonium salt of 2-acrylamido-2-methylpropanesulfonic acid and, if desired;

a stage (f) of purification of the comb copolymer obtained in stage (e).

tert-Butanol/water mixture denotes, in the process as defined above, a mixture for which the proportion by volume of water is less than or equal to 50%.

According to a specific aspect of the process as defined above, in the formula (II), R₂ and R₃ each represent a hydrogen atom and R₄ represents an isopropyl radical.

Another subject matter of the invention is a comb copolymer, the backbone of which is of the 2-acrylamido-2-methylpropanesulfonic acid type, to which poly(N-alkyl-(meth)acrylamide) or poly(N,N-dialkyl(meth)acrylamide) side segments are grafted, said side segments being chosen from the following side segments:

poly(N-methylmethacrylamide) side segments,

poly(N-ethylmethacrylamide) side segments,

poly(N-propylmethacrylamide) side segments,

poly(N-isopropylmethacrylamide) side segments,

poly[N-(2-hydroxyethyl)methacrylamide] side segments,

poly(N,N-dimethylmethacrylamide) side segments,

poly(N,N-diethylmethacrylamide) side segments,

poly(N-methylacrylamide) side segments,

poly(N-ethylacrylamide) side segments,

poly(N-propylacrylamide) side segments,

poly(N-isopropylacrylamide) side segments,

poly[N-(2-hydroxyethyl) acrylamide] side segments,

poly(N,N-dimethylacrylamide) side segments,

poly(N,N-diethylacrylamide) side segments,

and more particularly a comb copolymer as defined above in which said side segments are chosen from the following side segments:

poly(N-isopropylacrylamide) side segments,

poly[N-(2-hydroxyethyl)acrylamide] side segments,

poly(N,N-dimethylacrylamide) side segments and

poly(N,N-diethylacrylamide) side segments.

The following example illustrates the invention without, however, limiting it. It demonstrates that it is possible to prepare comb polymers without an acrylamide backbone comprising side segments of N-alkylacrylamide type which are heat-thickening.

Preparation of a Comb Copolymer Comprising a Backbone of ATBS Type, to Which poly(N-isopropylacrylamide) Side Segments are Grafted ATBS-g-NIPAM

(1) Preparation of a Poly(N-isopropyl Acrylamide) Telomer

435 g of N-isopropylacrylamide (NIPAM) are dissolved in a tert-butanol/water mixture (50/50 by volume) in a thermostatically controlled reactor until 1000 g are reached, and stirring is carried out under nitrogen sparging for approximately one and a half hours. 2-Aminoethanethiol hydrochloride (AET.HCl) is subsequently added in a predetermined NIPAM/AET.HCl molar ratio of approximately 48/1. The polymerization is initiated with dilauroyl peroxide by bringing the temperature to 60° C. and then the reaction medium is left stirring and under nitrogen sparging for a further 2 hours. A white and pasty final reaction mixture is obtained.

(2) Preparation of the Macromonomer

A solution of potassium hydroxide (0.16 N) in tert-butanol and acryloyl chloride are added to the reaction medium obtained in stage (1) maintained at a temperature of 10° C., while maintaining the pH in the vicinity of 9. At the end of the reaction, the content of NIPAM macromonomer is 17.8% by weight and the water content is 10.7% by weight.

(3) Synthesis of the Copolymer

61.8 g of the reaction medium obtained in stage (2) are diluted in 170 g of tert-butanol in the reactor thermostatically controlled at 15° C. 77 g of the ammonium salt of 2-acrylamido-2-methylpropanesulfonic acid and then 0.44 g of trimethylolpropane triacrylate are added thereto. The polymerization is initiated with dilauroyl peroxide and the medium is left stirring for four hours while maintaining the temperature at 60° C. The polymer which precipitated during the polymerization is recovered by filtration. After drying, the desired copolymer is obtained in the powder form.

It is found that a 1% by weight solution of the polymer in water is slightly viscous. After heating above 80° C., there is formation of a gel, which is characteristic of a heat-thickening polymer. 

1. A process for the preparation of a comb copolymer, the backbone of which is of the 2-acrylamido-2-methylpropanesulfonic acid type, to which poly(N-alkylacrylamide) or poly(N,N-dialkylacrylamide) side segments are grafted, characterized in that it comprises the following successive stages: a stage (a) of reaction of a compound of formula (II): CH₂═C(R₂)—C(═O)—N(R₃)(R₄)   (II) in which R₂ represents a hydrogen atom or a methyl group, R₃ represents a hydrogen atom or a linear or branched alkyl radical comprising from 1 to 4 carbon atoms and R₄, which is identical to or different from R₃, represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, with a chain-limiting compound of formula (III): Z—R₁—NH₂   (III) in which R₁ represents a divalent radical comprising from 1 to 4 carbon atoms and Z represents a functional group capable of acting as radical transfer agent, in the presence of a polymerization initiator, in a tert-butanol/water mixture, in order to obtain a poly(N-alkylacrylamide) or poly(N,N-dialkylacrylamide) telomer of formula (I): H₂N—R₁—Z—{CH₂—C(R₂)[C(═O)N(R₃)(R₄)]—}_(n)—H   (I) in which n represents an integer greater than or equal to 2 and less than or equal to 100 and Z represents a functional group capable of acting as radical transfer agent; optionally a stage (b) of isolation and/or of drying of said telomer of formula (I) obtained in stage (a); a stage (c) of reaction in tert-butanol of the telomer of formula (I) obtained in stage (a) or optionally in stage (b) with an acid chloride of formula (IV): CH₂═C(R₅)—C(═O)—Cl   (IV) in which R₅ represents a hydrogen atom or a methyl radical, in a (IV)/(III) molar ratio of less than or equal to 10 and greater than or equal to 1, while maintaining the pH of the reaction medium at a value of between 8 and 10, in order to obtain a solution of the macromonomer of formula (V): CH₂═C(R₅)—C(═O)NH—R₁—Z—{CH₂—C(R₂)[C(═O)N(R₃)(R₄)]—}_(n)—H   (V) optionally a stage (d) of isolation and/or of drying of said macromonomer of formula (V) obtained in stage (c); a stage (e) of copolymerization in tert-butanol of the macromonomer of formula (V) resulting from stage (c) or from stage (d) with the ammonium salt of 2-acrylamido-2-methylpropanesulfonic acid and, if desired; a stage (f) of purification of the comb copolymer obtained in stage (e).
 2. The process as defined in claim 1, for which, in the formula (II), R₂ and R₃ each represent a hydrogen atom and R₄ represents an isopropyl radical.
 3. A comb copolymer, the backbone of which is of the 2-acrylamido-2-methylpropanesulfonic acid type, to which poly(N-alkylacrylamide) or poly(N,N-dialkylacrylamide) side segments are grafted, said side segments being chosen from the following side segments: poly(N-methylmethacrylamide) side segments, poly(N-ethylmethacrylamide) side segments, poly(N-propylmethacrylamide) side segments, poly(N-isopropylmethacrylamide) side segments, poly[N-(2-hydroxyethyl)methacrylamide] side segments, poly(N,N-dimethylmethacrylamide) side segments, poly(N,N-diethylmethacrylamide) side segments, poly(N-methylacrylamide) side segments, poly(N-ethylacrylamide) side segments, poly(N-propylacrylamide) side segments, poly(N-isopropylacrylamide) side segments, poly[N-(2-hydroxyethyl) acrylamide] side segments, poly(N,N-dimethylacrylamide) side segments and poly(N,N-diethylacrylamide) side segments.
 4. The comb copolymer as defined in claim 3, in which said side segments are chosen from the following side segments: poly(N-isopropylacrylamide) side segments, poly[N-(2-hydroxyethyl)acrylamide] side segments, poly(N,N-dimethylacrylamide) side segments and poly(N,N-diethylacrylamide) side segments. 